Ind. Eng. Chem. Res.

1998, 37, 275-283 275

Vapor Pressure and Boiling Point Elevation of Slash Pine Black

Liquors: Predictive Models with Statistical Approach
A. A. Zaman,*,†,‡ T. W. McNally, and A. L. Fricke†
Department of Chemical Engineering, University of Florida, Gainesville, Florida 32611, and Engineering
Research Center for Particle Science and Technology, University of Florida, Gainesville, Florida 32611

Vapor-liquid equilibria and boiling point elevation of slash pine kraft black liquors over a wide
range of solid concentrations (up to 85% solids) has been studied. The liquors are from a
statistically designed pulping experiment for pulping slash pine in a pilot scale digester with
four cooking variables of effective alkali, sulfidity, cooking time, and cooking temperature. It
was found that boiling point elevation of black liquors is pressure dependent, and this dependency
is more significant at higher solids concentrations. The boiling point elevation data at different
solids contents (at a fixed pressure) were correlated to the dissolved solids (S/(1 - S)) in black
liquor. Due to the solubility limit of some of the salts in black liquor, a change in the slope of
the boiling point elevation as a function of the dissolved solids was observed at a concentration
of around 65% solids. An empirical method was developed to describe the boiling point elevation
of each liquor as a function of pressure and solids mass fraction. The boiling point elevation of
slash pine black liquors was correlated quantitatively to the pulping variables, using different
statistical procedures. These predictive models can be applied to determine the boiling point
rise (and boiling point) of slash pine black liquors at processing conditions from the knowledge
of pulping variables. The results are presented, and their utility is discussed.

1. Introduction made at a liquor-to-wood ratio of 4/1. In all cases, the

Knowledge of black liquor equilibrium vapor pressure
and boiling point rise over wide ranges of temperature
and nonvolatile solids concentration is of particular
importance for the development and design of kraft
recovery components. These properties vary consider-
ably with the solids concentrations (and solids composi-
tion) and, therefore, become more critical at higher
solids concentrations as more evaporation stages are
required to achieve higher solids concentrations and to
increase performance characteristics of the evaporation
units. Accurate vapor pressure data and boiling point
rise data are necessary for design and operation of
evaporators for black liquor concentration to high solids.
The present knowledge of the vapor pressure data and
boiling point elevation of black liquors is incomplete due
to the variation with pulping conditions, black liquor
composition, solids concentration, and type of the wood
species. Past research has not established methods that
can be used to estimate vapor pressure or boiling point
rise at processing conditions from knowledge of pulping
conditions and/or black liquor composition.
In this paper, we report results on equilibrium vapor
pressure and boiling point rise-concentration-temper-
ature relations for softwood slash pine black liquors
based on data obtained for liquors derived from statisti-
cally designed pulping experiments that were conducted
in a pilot scale digester with liquor circulation. The
cooking variables were effective alkali, sulfidity, cooking
temperature, and cooking time, and the cooks were
* To whom correspondence should be addressed. Phone:
(352) 392-6509. Fax: (352) 392-9513. E-mail: zaman@
eng.ufl.edu.
† Department of Chemical Engineering.
‡ Engineering Research Center for Particle Science and
Technology.
S0888-5885(97)00531-9 CCC: $15.00 © 1998 American Chemical Society
Published on Web 01/05/1998
white liquor was adjusted to a causticizing efficiency of
85% and a reduction of 93% with Na2CO3 and Na2SO4.
The details of the pulping procedure and experimental
results have been reported in several earlier publica-
tions (Fricke 1987, 1990, 1993; Zaman et al., 1991).
The purpose of this research was to develop a con-
sistent set of vapor pressure and boiling point elevation
data for slash pine black liquors. We were interested
in the following: (1) the variation of vapor pressure and
boiling point rise with increasing solids concentration,
especially at high solids content where the solubility
limit of some of the components in black liquor is
exceeded; (2) the variation of these properties with solids
composition and pulping variables; and (3) development
of statistically based quantitative models for these
variables as a function of the pulping conditions.
A series of well-characterized liquors covering a wide
range of pulping conditions were used to generate data
for vapor pressure properties of black liquors. These
data were used to study the effect of pulping variables
on the boiling point rise of black liquors and to develop
predictive models as a function of the cooking conditions.
The results are presented, and their utility is discussed.
2. Overview and Background
In an earlier paper (Stoy et al., 1992), we reported
the results on the development of an apparatus (small-
scale evaporator) that was successfully applied for direct
determination of black liquor vapor pressures that were
thermodynamically consistent with treatment of black
liquor as a pseudobinary system. Boiling point data at
different pressures were directly determined with this
system over a wide range of concentration up to 85%
solids, depending upon the viscosity of the liquor. It
was observed that the boiling point elevation is pressure
dependent at concentrations above about 20% solids.
276 Ind. Eng. Chem. Res., Vol. 37, No. 1, 1998
The boiling point rise varies from liquor-to-liquor due
to the differences in the composition of the liquors, and
this dependency is more significant at higher solids
concentrations.
Several other methods have been reported in the
literature for measuring the vapor pressure of black
liquors, and these are briefly reviewed here. Kobe and
Sorenson (1939) have reported boiling point data for
black liquors up to 63% solids at different pressures.
Frederick et al. (1980) reported boiling point elevation
data at atmospheric pressure for black liquors at solids
concentrations up to about 65% solids. These research-
ers have used direct measurement techniques in which
the liquor is heated continuously, the boiling point is
recorded, and the resulting condensate is measured to
determine the solids concentration of the remaining
liquor in the vessel. The accuracy of their technique is
questioned due to the fact that liquor and water vapor
were probably not at equilibrium under the conditions
used, and superheating of the liquor at higher solids
concentrations was reported to be a problem. Some
researchers (Arlt and Onken, 1982; Thomas et al., 1982)
have tried to modify this technique by circulating the
liquor to achieve equilibrium, but the method does not
seem to be successful at high solids concentrations
where the viscosity is the main limiting factor.
Clay and Karnofski (1981) used a pilot scale flash
evaporator to determine the boiling point elevation for
black liquors dispersed in an immiscible oil. With this
technique, they were able to measure the boiling point
of black liquors for solids concentrations up to almost
100% solids. Although this method is potentially oper-
able up to dry solids, superheating of the liquid phase
appears to be a problem, especially in the case of two
immiscible liquids, leading to an overestimate of boiling
point elevation. Clay and Grace (1984) used a labora-
tory evaporator operating at total reflux and atmo-
spheric pressure to determine the boiling point elevation
for one black liquor dispersed in oil. All their experi-
ments were conducted at atmospheric pressure, and oils
of different volatility were used to alter the partial
pressure of water vapor in the liquid-oil systems.
Wennberg (1985) determined the boiling point for
sulfate liquors at concentrations from 55% to almost
100% solids. In his procedure, the water was evapo-
rated continuously from the liquor, the temperature of
the liquor was recorded, and the evaporated water was
condensed and measured to determine the solids con-
centration of the liquor in the evaporator. These results
are suspicious due to the following: (1) the fact that the
liquor may not be at thermal equilibrium in the absence
of total reflux and (2) the liquor phase is superheated,
especially at high solids concentrations where the
convective heat transfer rate is decreased considerably
by the very large increase in viscosity of the liquor at
high solids concentrations.
Some researchers (Szymonski and Grace, 1985; Rob-
inson and Clay, 1986) have used equilibrium gravimet-
ric techniques to determine the vapor pressure of black
liquors. A known mass of black liquor was coated on a
brass screen and then suspended over a saturated salt
solution at constant temperature and allowed to equili-
brate. The equilibrium solids content was determined
by a mass balance on the screen after equilibrium had
been established and the water vapor pressure was
calculated from the known saturation pressure of the
salt solution. The results are uncertain due to problems
of temperature control, reaction with the brass screen,
and water adsorption by the screen, especially at very
high solids. Robinson and Clay (1986) determined the
boiling point rise of one black liquor above 85% solids
at atmospheric pressure by suspending a pan of dry
black liquor in a steam chamber (containing steam at
atmospheric pressure) with a calibrated quartz spring.
The chamber was placed in a temperature-controlled
oven. At a fixed temperature, the water vapor was
absorbed by black liquor, and at equilibrium conditions,
the mass of the liquor in the pan was measured and
the solids concentration of the liquor was determined
by a mass balance. Although this method seems to be
the best for determining vapor pressure of black liquors
at high solids concentrations, it should be mentioned
that the true equilibrium may not be achieved in
reasonable times due to the slow diffusion of water
vapor into the layer of black liquor in the pan. Also,
the method of drying used to achieve dry black liquors
may affect the nature of 100% black liquor solids.
3. Materials
The black liquors used in this study are from a four-
variable, two-level central composite design for pulping
slash pine. Kraft pulping of slash pine was conducted
in a pilot scale digester of total volume of 0.1 m3
operated with liquor circulation. The four pulping
variables were effective alkali (EA), sulfidity (S), cooking
temperature (T), and time at temperature (t), respec-
tively. The effective alkali is defined as NaOH + 1/2-
Na2S, expressed as Na2O, and the sulfidity is defined
as Na2S/(NaOH + Na2S), expressed as Na2O (Casey,
1980). The range of the variables used in the design
were 11.5-17.5% for EA, 12.5-42.5% for S, 160.0-
182.2°C for cooking temperature, and 20-60 min for
cooking time. The liquor-to-wood ratio was fixed at 4/1,
and the white liquor was adjusted with sodium carbon-
ate and sodium sulfate to a causticizing efficiency of 85%
and a reduction of 93%.
After cooking, black liquor was quickly drained. The
pulp was washed twice with water at 80 °F, and the
two washes were combined with the black liquor. The
combined liquor and washes were filtered to remove all
fibers from the liquor, and samples of black liquor and
washed pulp were taken for analysis. Black liquor
solids were measured using TAPPI method T650 PM-
84. A sufficient amount of black liquor was loaded into
the small-scale evaporator to determine the boiling point
of the liquor as a function of pressure and solids mass
fraction.
4. Brief Description of the Small-Scale
Evaporator Apparatus and Experimental
Procedure
Details of the design of the apparatus and its sche-
matic have been given in an earlier publication (Stoy
et al., 1992). The basic apparatus is a 5 L still pot with
three main parts: a glass sleeve, glass top, and stainless
steel bottom. The top contains openings for the stirrer,
condenser, pressure transducer, and a platinum resis-
tance thermometer. The bottom clamps to the bottom
of the glass sleeve and contains baffles and a drain port.
The bottom can be removed for cleaning without dis-
turbing the rest of the apparatus. Heating is provided
by an electric jacket that slides over the stainless steel
bottom, and the heating rate is controlled by controlling
 Ind. Eng. Chem. Res., Vol. 37, No. 1, 1998 277
the voltage of the electric jacket. The heat input can Table 1. Pulping Conditions for the Liquors Used in
be varied to produce up to 30 mL/min condensate but This Studya
is usually operated to give 1-5 mL/min of condensate. cook no. t, min T, K EA, % S, %
The pressure control system consists of a PID controller, ABAFX011,12 40 438.75 13 20
pressure transducer, bleed valve, and a vacuum pump. ABAFX013,14 80 449.85 13 20
The controller operates the bleed valve, which is con- ABAFX015,16 80 438.75 16 20
nected between the vacuum pump and still to control ABAFX019,20 80 438.75 13 35
the pressure in the still. Turbine blade stirrers con- ABAFX021,22 40 449.85 13 35
nected to a variable-speed D.C. motor are used for ABAFX023,24 40 438.75 16 35
ABAFX025,26 80 449.85 16 35
mixing. Stirrer speed can be varied from 0 to 300 rpm, ABAFX029,30 40 449.85 13 20
and the direction of stirring is reversible. A stuffing ABAFX031,32 40 438.75 16 20
box, filled with Teflon packing, seals the stirrer shaft ABAFX033,34 80 449.85 16 20
to prevent air leakage into the system. The tempera- ABAFX037,38 80 449.85 13 35
ture of the liquor is measured with a platinum resis- ABAFX039,40 80 438.75 16 35
ABAFX043,44 60 444.25 14.5 27.5
tance thermometer that is connected to a Rosemount
ABAFX053,54 60 444.25 11.5 27.5
414L (P) transducer bridge to produce a signal of 1 mV/ ABAFX055,56 60 444.25 17.5 27.5
°C output that is read with a digital voltmeter. The ABAFX059,60 60 444.25 14.5 42.5
evaporator is equipped with two condensers connected ABAFX067,68 60 444.25 14.5 12.5
in series. Therefore, the system can be used for either ABAFX069,70 60 433.15 14.5 27.5
concentrating the liquor or measuring the vapor-liquid ABAFX071,72 60 455.35 14.5 27.5
ABAFX075,76 20 444.25 14.5 27.5
equilibria under alternating cycles of total reflux and ABAFX077,78 40 449.85 16 20
evaporation. The operation can be changed by turning
a Key: t, cooking time; T, cooking temperature; EA, effective
the water on or off to the first condenser.
Before using this system for black liquors, the boiling alkali; S, sulfidity.
point of water was determined as a function of pressure
using this apparatus. Boiling points of water deter-
mined at pressures from 120 to 760 mmHg agreed with
the literature values to within (0.06 °C or better. Also,
sucrose solutions (up to 65% by weight) were used to
determine the effect of viscosity and solids concentra-
tions. Experimental boiling point measurements agreed
with literature values within (0.15 °C or better.
With black liquors, the liquor was concentrated from
the initial concentration at a low pressure (200 mmHg)
and a moderately high evaporation rate (8-12 mL/min).
When the desired concentration was reached, the evapo-
ration rate was reduced to 1-1.5 mL/min and the still
was operated at total reflux. While under constant
reflux, a series of boiling point versus pressure data
were taken by first setting the pressure and then Figure 1. Vapor pressure of experimental softwood kraft black
recording the temperature when equilibrium was at- liquor ABAFX025,26 at different solids concentrations.
tained. Equilibrium at each pressure was reached
normally in 15-30 min. When a complete data set was cal analysis of the samples of condensate indicated no
finished, the sample was concentrated to the next solids detectable salts and only traces of organic carbon;
concentration and the procedure repeated. A load cell therefore, the condensate was essentially water. It is
was used to record the amount of condensate produced important to note that the log plots of vapor pressure
during concentration, and the solids mass fraction in as a function of 1/T are nearly linear over the whole
the liquor was calculated from the mass balance. Also, range of solids concentrations for all liquors studied. If
at the end of each run, small samples of the liquor were we treat black liquor as a binary solution of organic and
taken to determine the final solids mass fraction, and inorganic components in water, at equilibrium condi-
this was compared with the mass balance result. tions, where the liquor and the water vapor are at
equilibrium with one another at vapor pressure, P, the
5. Results following relationship applies (Lewis and Randall,
1961):
5.1. Effect of Pressure and Solids Concentra-
tions. A large number of kraft black liquors from dP ∆H
laboratory cooks of slash pine have been studied. The
(1)
dT T∆V
)
cooking conditions for these liquors are summarized in
Table 1. Overall, the behavior observed for all liquors where P ) pressure (atm), T ) absolute temperature
was similar. Figure 1 is a plot of vapor pressure as a (K), ∆H ) heat of vaporization, and ∆V ) the increase
function of temperature at different solids concentra- in volume when an amount of the substance vaporizes.
tions for one of the liquors used in this study that is a If we assume that the vapor phase is an ideal gas,
typical result. The vapor pressure decreases as the integrating eq 1 will yield
solids content increases, and its behavior with increas-
ing temperature is similar at all solids concentrations. B
ln(P) ) A - (2)
The liquors used in this work had been previously T
evaporated to 25-30% solids and the soap skimmed.
Therefore, volatile organics had been removed. Chemi- where A and B are constants. Equation 1 was applied
278 Ind. Eng. Chem. Res., Vol. 37, No. 1, 1998

Table 2. Parameters A and B as in Eq 2 for Three

Different Black Liquors
black liquor % solids A B R2
ABAFX011,12 17.8 13.54 5124.5 0.99
29.5 13.59 5091.9 0.99
34.9 13.52 5132.2 0.99
36.5 13.30 5145.5 0.99
43.1 13.52 5113.4 0.98
49.8 13.40 5114.6 0.99
56.4 13.22 5083.8 0.99
75.4 13.51 5269.3 0.97
84.1 13.48 5327.3 0.97
ABAFX013,14 23.6 13.45 5045.4 0.97
36.7 12.74 4814.2 0.97
47.4 12.96 4913.3 0.98
50.8 12.95 4931.1 0.99
59.1 13.31 5099.1 0.99 Figure 2. Boiling point elevation of experimental softwood kraft
67.2 12.83 4932.8 0.97 black liquor ABAFX063,64 at two pressures.
70.0 13.27 5114.9 0.98
75.0 12.83 4976.1 0.98
ABAFX025,26 20.9 13.07 4894.9 0.97
36.7 13.04 4915.6 0.98
49.0 13.02 4947.1 0.99
57.7 12.94 4957.7 0.99
64.8 12.78 4945.8 0.97
71.2 13.32 5201.5 0.98
78.2 13.18 5187.7 0.99
81.7 12.77 5075.2 0.99

to fit the data successfully for all the liquors listed in

Table 1 over a wide range of solids concentrations. The
results for some of the liquors at different solids
concentrations are listed in Table 2. As can be observed,
both A and B vary with the solids concentrations and
type of the liquor. If the heat of vaporization were
constant, then there should not be variation in the
values of B for a particular liquor with changes in the
solids concentrations. However, our earlier work indi-
cates that black liquors are nonideal solutions (Stoy,
1992; Stoy and Fricke, 1994; Zaman et al., 1996; Zaman
and Fricke, 1996) and their heat of dilution (or mixing)
cannot be ignored in evaporation experiments. There-
fore, variation in the values of B are due to the nonideal
nature of black liquors.
The thermodynamic consistency of treating black
liquor as a binary solution was studied by Stoy (1992)
and Stoy and Fricke (1994). They determined fugacities
and vapor pressures for one liquor by using the enthalpy
data and one vapor pressure equilibrium value obtained
from direct measurements. They developed vapor pres-
sure equilibrium curves at different concentrations and
compared these to experimentally determined vapor
pressure equilibrium curves at different solids contents.
The agreement was very good. Thus, vapor pressures
can be determined from enthalpy data that are as
accurate as the measured values, and it is thermody-
namically consistent to treat black liquor as a pseudo-
binary solution.
5.2. Boiling Point Elevation. The boiling point
elevation for black liquors is defined as the difference
between the boiling point of black liquor solution and
that of pure water at the same pressure. Figure 2 shows
the boiling point elevation for one of the liquors as a
function of solids concentration at two pressures. It is
evident that the boiling point rise pressure dependency
is more significant at higher solids concentrations. This
plot is typical of all the results. At 80% solids, the
boiling point elevation for this liquor at atmospheric
pressure is 22 °C. Clay and Grace (1984) have reported
a value of 24.5 °C, and Szymonski and Grace (1985)
have reported a value of 30 °C for boiling point elevation
Figure 3. Boiling point elevation of three different experimental
softwood kraft black liquors at atmospheric pressure.
of black liquors. The range of boiling point elevation
determined for a large number of experimental liquors
as a function of solids concentration in this work are
generally lower than the values that are reported in the
literature by other investigators.
Figure 3 is a plot of boiling point rise as a function of
solids concentration at atmospheric pressure for three
of the liquors used in this study. It can be observed
that the boiling point rise is a function of the solids
composition and that the variation in boiling point rise
from liquor-to-liquor becomes larger as the solids con-
centration increases. At solids concentrations lower
than 35% boiling point elevation does not change
significantly with the solids composition in the liquor.
Using a binary solution assumption, the boiling point
elevation for black liquors can be described as (Wenn-
berg, 1985)
BPR ) KBm (3)
where BPR is the boiling point rise (°C), KB is a
constant, and m is the molality of the solution. Since
the molality of the liquor solution is proportional to the
dissolved solids in water, eq 3 can be written as
S
BPR ) K (4)
1-S
where S is the solids mass fraction and S/(1 - S) is the
ratio of solids to water. Equation 4 was applied by
Frederick et al. (1980) to fit the boiling point elevation
of black liquors to the solids mass fraction. Frederick
et al. (1980) and Wennberg (1985) have shown that eq
4 is valid for concentrations up to about 50% solids. At

Figure 4. Boiling point elevation as a function of the dissolved
solids for black liquor ABAFX019,20 at different pressures.
Figure 5. Boiling point elevation as a function of the dissolved
solids for black liquor ABAFX051,52 at different pressures.
Figure 6. Parameter a as in eq 5 as a function of pressure for
black liquor ABAFX059,60.
higher concentrations, a change in the slope of the line
was observed. Frederick et al. (1980) concluded that
the change in the slope is due to the solubility limit of
Na2SO4 and Na2CO3 in the liquor. Above the solubility
limit, Na2SO4 and Na2CO3 begin to precipitate, and as
a result, the ratio of the dissolved solids to water
increases more slowly above the solubility limit. Fred-
erick et al. (1980) observed that, above the solubility
limit, the boiling point of a particular black liquor did
not change by adding Na2CO3 to the liquor. This
indicates that the boiling point elevation depends only
on the dissolved solids and increases more slowly with
total solids content above the solubility limit. The solids
content at which the slope of the boiling point elevation
versus S/(1 - S) starts to change was taken to be the
solubility limit of Na2CO3 and Na2SO4 in black liquor.
Ind. Eng. Chem. Res., Vol. 37, No. 1, 1998 279
Figure 7. Parameters a′ and b′ as in eq 6 as a function of pressure
for black liquor ABAFX015,16.
Figures 4 and 5 demonstrate the variation of the
boiling point elevation with solids mass fraction to water
ratio S/(1 - S) at different pressures for two of the
liquors used in this study. Two distinguishable regions
of boiling point rise can be observed from these plots.
At high values of S/(1 - S), the slope of the curves
decreased significantly at all pressures. For all slash
pine kraft black liquors used in this study, the break
point occurs at concentrations around 65% solids. As
mentioned by Frederick et al. (1980), this is the solubil-
ity limit concentration for slash pine kraft liquors.
The lower and upper portions of boiling point eleva-
tion data for all liquors at each pressure were described
as a function of S/(1 - S) using the following equations:
(1) the lower portion:
S
BPR ) a (5)
1-S
(2) the upper portion:
S
BPR ) a′ + b′ (6)
1-S
where a, a′, and b′ are constants that are pressure
dependent and vary from liquor to liquor due to the
differences in the composition of the liquors.
It was found that the parameters a, a′, and b′ for
every single liquor have a linear relation with pressure,
as indicated in Figures 6 and 7, which are plots of these
parameters as a function of pressure. Figure 6 is a plot
of the constant a versus pressure for liquor ABAFX059,-
60, and Figure 7 shows plots of a′ and b′ versus
pressure. This is a very unique and interesting result
and can be used as a basis for data reduction and for
obtaining universal correlations for boiling point eleva-
tion of black liquors as a function of pressure and solids
concentration. These parameters were described as
a ) a1 + b1P (7)
a′ ) a2 + b2P (8)
b′ ) a3 + b3P (9)
where a1, b1, a2, b2, a3, and b3 are constants that are
composition dependent and P (mmHg) is pressure. By
280 Ind. Eng. Chem. Res., Vol. 37, No. 1, 1998

Table 3. Parameters a1, b1, a2, b2, a3, and b3 as in Eqs 7-9 for the Liquors Used in This Study
liquor a1 b1 R2 a2 b2 R2 a3 b3 R2
ABAFX011,12 6.4779 0.0027 0.99 6.4100 0.0039 0.98 2.4198 0.0001 0.95
ABAFX013,14 4.5268 0.0036 0.95 1.9760 0.0037 0.99 2.9903 0.0005 0.99
ABAFX015,16 4.8986 0.0058 0.99 4.9615 0.0030 0.99 2.9424 0.0012 0.97
ABAFX019,20 4.0383 0.0039 0.98 4.9886 0.0020 0.99 2.5190 0.0011 0.97
ABAFX021,22 2.9704 0.0052 0.97 1.0695 0.0032 0.99 3.8406 0.0006 0.92
ABAFX023,24 5.4163 0.0048 0.99 3.3479 0.0027 0.99 4.4275 0.0010 0.98
ABAFX025,26 4.7320 0.0040 0.98 2.5867 0.0061 0.98 3.6788 0.0003 0.91
ABAFX029,30 3.3071 0.0046 0.98 1.9893 0.0023 0.99 3.0659 0.0016 0.97
ABAFX031,32 5.5057 0.0037 0.98 9.1854 0.0032 0.96 1.6429 0.0012 0.99
ABAFX033,34 3.9646 0.0050 0.99 1.9807 0.0027 0.99 4.6920 0.0003 0.99
ABAFX037,38 3.7780 0.0033 0.98 3.2908 0.0047 0.98 2.6992 0.0007 0.99
ABAFX039,40 3.9872 0.0050 0.98 2.0465 0.0037 0.98 3.4490 0.0013 0.97
ABAFX043,44 4.8785 0.0038 0.98 3.8232 0.0042 0.96 3.3749 0.0009 0.96
ABAFX053,54 4.0645 0.0033 0.98 4.4454 0.0017 0.98 2.9695 0.0007 0.98
ABAFX055,56 4.7771 0.0042 0.99 4.9451 0.0017 0.98 3.2131 0.0017 0.98
ABAFX059,60 3.7005 0.0050 0.98 1.6317 0.0047 0.99 3.8420 0.0006 0.99
ABAFX067,68 6.6487 0.0024 0.97 4.3682 0.0034 0.98 3.2226 0.0002 0.99
ABAFX069,70 7.5405 0.0039 0.98 8.2448 0.0027 0.97 3.4371 0.0004 0.99
ABAFX071,72 5.4164 0.0036 0.98 3.3423 0.0034 0.98 2.6084 0.0007 0.98
ABAFX075,76 6.1824 0.0022 0.98 0.3336 0.0032 0.99 5.7703 0.0006 0.98
ABAFX077,78 7.5048 0.0033 0.98 3.2589 0.0032 0.99 4.1303 0.0006 0.98

Table 4. Complete Linear Regression Model Parameters for a1, b1, a2, b2, a3, and b3
parameters
variable a1 b1 a2 b2 a3 b3
intercept 4540.587 1.662954 2383.602 1.724884 -3927.78 -0.96978
t -16.2538 -0.02459 2.368055 -0.06696 80.05616 -0.00879
T -16.1168 -0.0055 -12.4561 7.03 × 10-5 10.01004 0.003514
EA -158.044 -0.06679 92.30174 -0.24535 196.7819 0.030668
S -23.1972 -0.04131 30.13235 -0.10507 132.8823 0.004923
Tt 0.038256 5.46 × 10-5 -0.00497 0.000152 -0.17875 1.87 × 10-5
tEA 1.552048 0.001758 -0.46844 0.004644 -4.94237 0.000504
tS 0.144971 0.000853 0.010979 0.001875 -2.74947 0.000309
TEA 0.366594 0.000147 -0.21085 0.000576 -0.43624 -7.5 × 10-5
TS 0.055112 9.33 × 10-5 -0.06784 0.000241 -0.29599 -1.3 × 10-5
EAS 2.723327 0.003052 -3.04463 0.007878 -7.95667 -0.00055
t2 -0.00035 -1.21 × 10-8 -0.00181 -4.3 × 10-7 0.001477 -3.3 × 10-7
T2 0.013012 4.04 × 10-6 0.015983 -9.3 × 10-6 -0.00282 -2.8 × 10-6
EA2 -0.06044 1.65 × 10-5 0.096815 -0.00028 -0.03122 3.33 × 10-5
S2 0.001154 -2.3 × 10-7 -0.00366 -6.7 × 10-7 0.000711 -2.2 × 10-6
tTEAS 6.68 × 10-5 1.34 × 10-7 -1.6 × 10-5 3.17 × 10-7 -0.00038 3.35 × 10-8
TEAS -0.00634 -6.9 × 10-6 0.006832 -1.8 × 10-5 0.017748 1.38 × 10-6
tEAS -0.0282 -6 × 10-5 0.006587 -0.00014 0.17061 -1.6 × 10-5
tTEA -0.0036 -3.9 × 10-6 0.001043 -1.1 × 10-5 0.011022 -1.1 × 10-6
tTS -0.00038 -1.9 × 10-6 0 -4.3 × 10-6 0.006124 -6.6 × 10-7
R2 0.99 0.99 1.0 1.0 0.98 1.0

substituting eq 7 in eq 5 and eqs 8 and 9 in eq 6, the
boiling point elevation of each slash pine kraft black
liquor as a function of solids mass fraction and pressure
can be defined as
S experiment with center and star points for kraft pulping
BPR ) (a1 + b1P) for S < 0.65 (10)
1-S
S responses and for obtaining proper predictive models
BPR ) (a2 + b2P) + (a3 + b3P) for S g 0.65
1-S
(11)
The constants a1, b1, a2, b2, a3, and b3 were determined
for all slash pine kraft black liquors used in this study,
and these are listed in Table 3. As can be observed,
the R2 of the fits are very high which indicates that the
fits are very accurate. These constants vary from liquor
to liquor due to the fact that the liquors are composi-
tionally different. Since the effects of pressure and
solids mass fraction can be combined together and the
boiling point elevation can be defined with a single
correlation of these variables, the effects of solids
composition arising from differences in pulping condi-
tions can be partitioned and the constants of the model
for each liquor can be used to study the effect of the
pulping conditions on boiling point elevation of black
liquors.
As described earlier, the liquors used in this study
are from a two-level, four-variable factorially designed
of slash pine. The resulting rotatable composite design
supplies enough information for determining nonlinear
for the constants of eqs 10 and 11 as a function of
pulping conditions that can be applied to determine the
boiling point rise and boiling point for other slash pine
black liquors. One of the main objectives of the current
study was to represent proper correlations that can be
applied to estimate the boiling point rise and boiling
point of black liquors at operating conditions from the
knowledge of pulping variables. To date, no similar
study has been reported in the literature.
In order to obtain predictive models for boiling point
elevation of slash pine kraft black liquors, different
statistical approaches were used to establish proper
models for a1, b1, a2, b2, a3, and b3 as a function of the
cooking conditions. By replacing these models in eqs

10 and 11, one can determine the boiling point elevation
for any slash pine kraft black liquor of known cooking
conditions at a desired pressure and solids concentra-
tion.
5.3. Statistical Modeling. In order to investigate
the influence of the cooking conditions on boiling point
rise of slash pine black liquors and obtain proper
predictive models, different statistical approaches were
used to develop these models for a1, b1, a2, b2, a3, and
b3 as a function of the pulping variables. As a basis for
model selection, the following linear regression model
that consists of the main variables, second-, third-, and
fourth-order interactions, and quadratic terms was
employed
4 4 4
Y ) β0 + ∑ βiXi + ∑ βijXiXj + ∑ βijkXiXjXk +
i)1 i<j i<j<k
4 4
∑
i<j<k<l
βijklXiXjXkXl + ∑
i)l
βiiXi2
where Y is the estimate for the independent variables
(a1, b1, a2, b2, a3, b3) and Xi’s are the independent
variables (EA, S, T, and t) known for each cook. The
constants β0, βi, βij, βijk, βii, and βijkl are the regression
parameters. Xi’s are the main variables, XiXj’s are
second-order interactions, XiXjXk’s are third-order in-
teractions, XiXjXkXl’s are fourth-order interactions, and
XiXi terms account for the quadratic effects. The model
contains four linear terms, six second-order interaction
terms, four third-order terms, one fourth-order interac-
tion term, four quadratic terms, and one constant term,
a total of 20 parameters in the model. The model
parameters for the independent variables using the full
regression model are shown in Table 4.
All the variables used in eq 12 are not reasonable
candidates as independent variables. Different selection
procedures were employed to select the proper indepen-
dent variables for a predictive model, and these are
discussed in many references (e.g., Box, 1978; Ott, 1988).
The first selection procedure was involved in performing
all possible regressions with the dependent variables
and one or more of the independent variables used in
eq 11. The RSQUARE procedure in SAS with Mallow’s
Cp criterion was used to perform statistical analyses for
variable selection of a1, b1, a2, b2, a3, and b3 as a function
of the pulping variables. This procedure finds subsets
of independent variables that best predict a dependent
variable by linear regression in the given sample (SAS
manual, 1985) and can be set to perform all possible
subset regressions. This procedure indicates that the
best fit without bias can be obtained with 11 variables.
The RSQUARE procedure is used for exploratory model
analysis and requires running a large number of regres-
sion models and can be very time consuming.
Another selection method that gives insight into the
relationship between the dependent and independent
variables and was employed in this work for model
selection was the stepwise procedure in SAS with
forward selection, backward elimination, and maximum
R2 strategy. The predictive models for a1, b1, a2, b2, a3,
and b3 were chosen using the above procedures. The
predicted values and the corresponding residuals were
determined using a regression procedure (REG) in the
SAS statistics system. The predictive models are as
follows:
Ind. Eng. Chem. Res., Vol. 37, No. 1, 1998 281
a1 ) 3.955 × 103 + 2.941t - 15.278T - 77.690EA -
5.470 × 10-3Tt - 3.488 × 10-2tEA - 0.397tS +
0.178TEA + 1.428 × 10-2T2 - 5.0 × 10-5tTEAS +
2.260 × 10-2tEAS + 8.750 × 10-4tTS with
R2 ) 0.93 and adjusted R2 ) 0.84 (13)
b1 ) 5.772 × 10-1 + 1.288 × 10-3t - 3.260 ×
10-3T + 1.625 × 10-2EA + 1.110 × 10-4S -
3.198 × 10-6tT - 1.655 × 10-6tS - 3.936 ×
10-5TEA + 1.50 × 10-7t2 + 4.480 × 10-6T2 +
2.255 × 10-5EA2 + 2.734 × 10-8tTEA
with R2 ) 0.98 and adjusted R2 ) 0.96 (14)
a2 ) 3.778 × 103 - 17.7T + 38.72EA + 2.861 ×
10-1tS - 9.448 × 10-2TEA - 2.894 × 10-2EAS -
1.315 × 10-3t2 + 2.082 × 10-2T2 + 1.633 ×
(12)
10-1EA2 + 5.621 × 10-5tTEAS - 2.537 ×
10-2tEAS - 6.190 × 10-4TtS
with R2 ) 0.97 and adjusted R2 ) 0.94 (15)
b2 ) 1.558 + 5.050 × 10-4t + 6.930 × 10-3T +
9.266 × 10-3EA - 3.721 × 10-5tEA - 8.177 ×
10-5tS + 2.113 × 10-6TS - 7.054 × 10-5EAS -
8.079 × 10-6T2 - 2.610 × 10-4EA2 + 1.514 ×
10-6tEAS + 1.390 × 10-7tTS
with R2 ) 0.95 and adjusted R2 ) 0.88 (16)
a3 ) -6.745 × 102 + 3.314t - 15.790EA + 3.905S -
2.990 × 10-4tT - 3.376 × 10-3tS + 3.812 ×
10-2EAS - 8.249 × 10-3TS + 9.910 × 10-4t2 -
4.070 × 10-3T2 - 4.873 × 10-2EA2 + 1.460 ×
10-5tTEA
with R ) 0.81 and adjusted R2 ) 0.78 (17)
2
b3 ) -8.334 × 10-3 - 1.736 × 10-2t + 2.161 ×
10-5T + 3.869 × 10-5tT + 1.120 × 10-3tEA +
4.640 × 10-4tS - 3.360 × 10-7t2 - 1.566 ×
10-6S2 + 6.405 × 10-8tTEAS - 2.876 ×
10 tEAS - 2.496 × 10-6tTEA - 1.029 × 10-6tTS
-5
with R2 ) 0.80 and adjusted R2 ) 0.75 (18)
In the above equations, time (t) is in minutes, tem-
perature (T) is in K, and effective alkali (EA) and
sulfidity (S) are in percent. The residual analysis of
these models indicates that these models are accurate
to within about (4% or better for boiling point rise.
6. Construction of Vapor
Pressure-Temperature Charts
In order to develop data for the boiling point of slash
pine black liquors from known cooking conditions, the
following procedure can be applied:
(1) Determine parameters a1, b1, a2, b2, a3, and b3 from
eqs 13-18 for a liquor of particular cooking conditions.
(2) Replace these in eqs 10 and 11 to determine the
boiling point rise as a function of pressure and solids
mass fraction. At a fixed value of solids mass fraction,
determine BPR at different pressures. At each pres-
282 Ind. Eng. Chem. Res., Vol. 37, No. 1, 1998
Figure 8. Comparison between the calculated and observed
values of vapor pressure for black liquor ABAFX043,44.
Figure 9. Comparison between the calculated and observed
values of vapor pressure for black liquor ABAFX051,52.
sure, determine the boiling point of the liquor from the
boiling point of water at the same pressure. Use eq 10
for S < 0.65 and eq 11 for S g 0.65.
The above procedure was employed to determine the
boiling point of two liquors used in this work at different
solids concentrations and pressures. The calculated
values using this procedure (solid lines) are compared
with experimental observations (symbols) in Figures 8
and 9, which are plots of vapor pressure as a function
of 1/T for liquors ABAFX043,44 and ABAFX051,52.
Liquor ABAFX043,44 was included in model selection
and liquor ABAFX051,52 was excluded. The calculated
values and experimental observation agree with each
other to (4% or better.
7. Summary and Conclusions
In this work, the vapor pressure and boiling point rise
data for slash pine kraft black liquors over a wide range
of solids concentration are presented. Direct measure-
ment of black liquor vapor pressures were made with
an apparatus that was developed prior to this work. The
results are accurate and thermodynamically consistent
with treatment of black liquor as binary solution of
solids in water. It is shown that the boiling point
elevation at a specific pressure can be correlated to the
dissolved solids in black liquor. However, around 65%
solids, a decrease in the slope of the boiling point
elevation as a function of the dissolved solids was
observed. This is due to the solubility limit of some of
the salts in black liquor.
The effects of pulping variables on boiling point rise
of slash pine black liquors were studied quantitatively
by different statistical strategies. Accurate empirical
models were developed for boiling point rise as a
function of pressure and solids concentrations that can
be used to predict boiling point rise of the liquors at
operating conditions. Comparison between the calcu-
lated values of boiling point rise and vapor pressure
determined from the correlations that are presented in
this paper, and the observed values indicate that the
models should be accurate to within (4% or better over
wide ranges of solids mass fraction and pressure.
While the results described here are for slash pine
kraft black liquors, the principles developed are gener-
ally applicable with few exceptions to other liquors. The
methods permit complete description of the vapor pres-
sure and boiling point rise of a kraft black liquor over
wide ranges of processing conditions. Less experimental
data would be required to describe the vapor pressure
and boiling point rise of the liquors from other wood
species.
Acknowledgment
Support provided by the U.S. Department of Energy
under Grant No. DE-FG02-85ER40740 and the Uni-
versity of Florida Engineering Research Center for
Particle Science and Technology is gratefully acknowl-
edged. We are also grateful for the assistance of Mr. S.
Tavares, Mr. A. Preston, and Mrs. B. Speck.
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Received for review July 28, 1997
Revised manuscript received October 14, 1997
Accepted October 15, 1997X
IE9705315
X
Abstract published in Advance ACS Abstracts, December
15, 1997.